US4719124A - Low temperature deposition utilizing organometallic compounds - Google Patents
Low temperature deposition utilizing organometallic compounds Download PDFInfo
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- US4719124A US4719124A US06/851,255 US85125586A US4719124A US 4719124 A US4719124 A US 4719124A US 85125586 A US85125586 A US 85125586A US 4719124 A US4719124 A US 4719124A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02387—Group 13/15 materials
- H01L21/02395—Arsenides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/024—Group 12/16 materials
- H01L21/02411—Tellurides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02562—Tellurides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
Definitions
- This invention relates to the deposition of semiconductor materials and, in particular, the deposition of semiconductor materials utilizing organometallic compounds.
- II-VI semiconductor materials in infrared detection devices, such as devices utilized for observing objects in low light surroundings, has generated substantial interest. Additional interest has been generated by the contemplated use of these material in applications such as detectors and lasers for optical fiber communications.
- the II-VI material must, during the fabrication process, be deposited on a mechanically stable structure, i.e., a substrate.
- This deposition of semiconductor materials such as II-VI semiconductor materials, e.g., cadmium telluride, mercury telluride, cadmium sulfide, zinc selenide and mercury cadmium telluride, is, in one method, accomplished by a metal-organic chemical vapor deposition procedure (MOCVD). In this procedure a deposition vapor flow containing at least one organometallic compound is established, and deposition is induced by interaction with the heated substrate.
- MOCVD metal-organic chemical vapor deposition procedure
- cadmium telluride has been deposited by passing a combination of dimethylcadmium and either dimethyltelluride or diethyltelluride over a substrate heated to a temperature typically in the range 340° C. to 420° C.
- various procedures have been developed for the deposition of cadmium mercury telluride utilizing precursors such as elemental mercury, dimethylcadmium, and diethyltelluride.
- the precursor material for depositing the first layer is introduced and after deposition of sufficient material, this precursor is changed to induce the formation of subsequent overlying layers.
- interdiffusion occurs between adjacent layers or between the substrate and its overlying layer inducing degradation in device performance.
- low temperature deposition prevents interdiffusion and also limits the amount of volatile materials escaping from the layer being deposited. This latter effect is quite significant for deposited layers containing entities such as mercury with high vapor pressures.
- high precursor partial pressures are required to limit the extent of volatilization and thus to limit, in turn, control of device properties.
- use of high precursor concentrations is inconvenient because, for materials such as elemental mercury, the entire gas flow pathway must be heated to prevent condensation of the precursor before it reaches the substrate. Additionally, for materials such as dimethylmercury use of high concentration is not economic.
- each organometallic precursor that undergoes substantial decomposition only at temperatures above 300° C. should be precracked, i.e., the organometallic compound should be sufficiently decomposed to yield a partial pressure of the metal (or molecular fragment containing the metal) that is greater than or equal to the vapor pressure of that metal in the growing film at the substrate temperature, and (2) the resulting entities that are to be introduced into the deposited layer should be reacted with the remaining reactive precursor substances only at the substrate.
- cadmium mercury telluride in the deposition of cadmium mercury telluride, it is possible to deposit at a temperature in the range 220° C. to 300° C. by precracking diethyltellurium and dimethylmercury.
- the resulting decomposition products are not contacted with the cadmium precursor, e.g., dimethylcadmium, except on the substrate surface.
- Premature contact induces disadvantageous powder formation of materials such as cadmium telluride.
- deposited layer quality as measured by infrared spectroscopy and Hall mobility is quite good.
- FIG. 1 is illustrative of an apparatus suitable for practices involving the invention, and;
- FIGS. 2-4 are illustrative of results achieved with the invention.
- Deposition is induced by contacting a substrate with a precursor mixture suitable for depositing the desired layer composition.
- the composition of the substrate is not critical.
- a single crystal substrate such as a cadmium telluride or gallium arsenide single crystal.
- a substrate having various layers such as cadmium telluride layers previously deposited on a single crystal substrate.
- the substrate temperature is typically dictated by the materials utilized in the structure to be fabricated and the configuration of that structure. For example, a sufficiently low temperature should be utilized so that substantial interdiffusion of materials between the device layers is substantially avoided.
- a sufficiently low temperature should be utilized so that substantial interdiffusion of materials between the device layers is substantially avoided.
- Exemplary of situations where diffusion is not desirable is in devices such as lasers employing adjacent layers of differing mercury concentration, e.g., adjacent layers of CdTe/Hg 1-x Cd x Te/CdTe. In such devices, temperatures above 350° C. typically cause significant interdiffusion of mercury and thus, in turn, substantially degrade device performance.
- mercury compositons such as Hg 1-x Cd x Te are utilized
- temperatures below 350° C. are desirable to prevent the necessity of extremely high precursor gas concentration. Indeed, it is generally desirable for devices relying on II-VI semiconductor materials to deposit at temperatures below 300° C., preferably below 250° C.
- each organometallic material utilized which undergoes substantial decomposition only at temperatures above 300° C., should be precracked.
- reactive precursor gases that are not precracked and which ultimately form a substantial portion of the deposited material i.e., greater than 0.1 mole percent, should be contacted with the precracked materials only on the substrate.
- Precracking in the context of this invention, means decomposing the organometallic compound sufficiently to yield a partial pressure of the metal (or molecular fragment containing the metal) that is greater than or equal to the vapor pressure of that metal in the growing film at the substrate temperature.
- a reactive precursor in this context, is one that interacts with a cracking entity to form a non-gaseous product at the operating temperatures.
- Combination or reactive and precracked entities at an inappropriate spatial region generally results in the disadvantageous formation of powders in the gas stream.
- a suitable procedure for ensuring interaction at the substrate is achieved by using a rotating sample holder. The substrate is first rotated to intersect the flow of precracked entities. The substrate is then rotated out of this flow and into a flow of reactive precursor gases.
- Precursor gases are chosen so that they supply the appropriate entities for forming the desired device layer.
- Compounds such as dimethyl or diethylcadmium are useful for the deposition of layers containing cadmium atoms; compounds such as dimethyl or diethyl or diisopropyltelluride are useful for the deposition of layers containing telluride atoms; compounds such as elemental mercury, diethylmercury, and dimethylmercury are useful for the deposition of layers containing mercury atoms; and compounds such as diethylzinc are useful for the deposition of layers containing zinc atoms.
- the precursor is employed at a partial pressure in the range 0.001 Torr to approximately 30 Torr.
- the mole ratios of precursor compound are adjusted to yield the desired deposited layer stoichiometry. Generally, an appropriate mole ratio is determined by employing a control sample.
- the materials to be cracked are flowed through a heated tube, 11 in FIG. 1.
- the tube is heated to a temperature above the decomposition temperature of the precursor gas and is sufficiently long to ensure that precracking occurs.
- gases such as dimethylmercury and diethyltelluride
- temperatures in the range 350° C. to 450° C. are utilized, with heated tube lengths in the range 10 to 20 cm and gas velocities in the range 10 to 100 cm/sec.
- the precise parameters employed with a given reactor configuration, precursor gas composition, and substrate temperature are easily determined through the use of a controlled sample.
- Expedients should be employed to prevent the mixing of the precracked gas with materials that induce powder formation.
- a baffle such as shown in FIG. 1 at 14
- the use of this particular embodiment is not critical, and any expedient that prevents premature mixing to form powders is acceptable.
- Film deposition was carried out in a vertical cold wall MOCVD reactor (FIG. 1) containing a rotating graphite susceptor (silicon carbide coated), 15, heated with an rf induction coil, 16.
- the current setting for the rf power supply was fixed throughout each run; this current was used to obtain the desired substrate temperature.
- the deposition temperature was monitored by an infrared pyrometer and was monitored at approximately 250° C.
- the reactor pressure was maintained at 600 Torr by a pressure controller and a mechanical vacuum pump.
- the feed gases entered the reactor through two separate 6 mm diameter quartz tubes, 11 and 12.
- Dimethylmercury and diethyltelluride were flowed from one heated tube, 11, while dimethylcadmium was flowed from the other tube, 12.
- a baffle, 14 was placed between the two quartz tubes.
- the tube with flowing dimethylmercury and diethyltelluride was wrapped with a resistance wire for a distance of 15 centimeters.
- the energy for precracking the metalorganics was provided by the resistance wire and was controlled by regulating the current through the wire using a direct current power supply.
- the power input to the wire was about 100 watts.
- Dimethylmercury and dimethylcadmium bubblers were maintained at 0° C. and a diethyltelluride bubbler was maintained at 25° C. in constant temperature baths. These metalorganics were delivered to the reactor using hydrogen as a carrier gas. Typical flow rates of hydrogen through the dimethylmercury, dimethylcadmium and the diethyltelluride bubblers were kept at 25 sccm, 0.6 sccm and 4.8 sccm, respectively, by mass flow controllers. The metalorganic sources were further diluted about ten times by hydrogen gas.
- Semi-insulating (100) cadmium telluride substrates were cleaned by boiling in chloroform and acetone, rinsed in methanol, and then etched with a dilute bromine-methanol solution. The etched substrates were further rinsed with methanol and then blown dry with nitrogen. The substrate, 18, was then placed off-center on the susceptor, 15. The reactor was then sealed and evacuated to a pressure of approximately 10 mTorr. A hydrogen flow was initiated and the pumping speed was reduced to bring the reactor up to operating pressure. Only hydrogen was allowed to flow into the reactor while power was applied to the precracking tube, and while the substrate was allowed to stabilize at the desired growth temperature. The metalorganic flows were begun to initiate growth.
- the substrate alternately passed under (1) the heated tube carrying the precracked products of dimethylmercury and diethyltelluride and, (2) the tube carrying dimethylcadmium.
- Typical susceptor rotation speed was 100 rpm.
- a layer thickness of 4 ⁇ m was achieved after three hours. The flows were then terminated and the chamber evacuated. (Growth rates of between 1 to 2 ⁇ m/hr. were observed.)
- FIG. 2 Typical morphology of the resulting Hg 0 .7 Cd 0 .3 Te film is shown in FIG. 2.
- the surface was specular and has features similar to that of the substrate.
- the IR transmission spectra of these films is shown in FIG. 3. As indicated in FIG. 3, the IR transmission has very sharp cut-off edges.
- the measured films had thicknesses of about 4.0 ⁇ m.
- the material was n-type material with a room temperature Hall mobility of 12,200 cm 2 /V-sec and a carrier concentration of 2.7 ⁇ 10 17 /cm 3 . (A Hall mobility of 27,000 cm 2 /V-sec was obtained for a carrier concentration of 1.0 ⁇ 10 17 /cm 3 at 77° K.)
- Example I For growing multilayer structures, the procedure of Example I was followed. However, for the HgTe growth, a gas flow of dimethylmercury and diethyltelluride was introduced into the heated tube. For the CdTe growth, diethyltelluride was introduced into the heated tube while a gas flow of dimethylcadmium was introduced into the other tube. During the HgTe growth, the flow was established by utilizing 26 and 5 sccm hydrogen flows through dimethylmercury and diethyltelluride bubblers, respectively. During the CdTe growth, a hydrogen flow of 4 and 2 sccm through dimethylcadmium and diethyltelluride bubblers, respectively, was employed. Growth of each layer lasted 15 minutes. This procedure yielded HgTe/CdTe heterojunctions. A typical cross-section transmission electron micrograph of these heterojunctions (FIG. 4) shows an extremely sharp boundary.
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Abstract
Description
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US06/851,255 US4719124A (en) | 1986-07-28 | 1986-07-28 | Low temperature deposition utilizing organometallic compounds |
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US06/851,255 US4719124A (en) | 1986-07-28 | 1986-07-28 | Low temperature deposition utilizing organometallic compounds |
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US4719124A true US4719124A (en) | 1988-01-12 |
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US06/851,255 Expired - Lifetime US4719124A (en) | 1986-07-28 | 1986-07-28 | Low temperature deposition utilizing organometallic compounds |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4904337A (en) * | 1988-06-06 | 1990-02-27 | Raytheon Company | Photo-enhanced pyrolytic MOCVD growth of group II-VI materials |
US5685905A (en) * | 1995-03-10 | 1997-11-11 | Shin-Etsu Handotai, Co., Ltd. | Method of manufacturing a single crystal thin film |
US5998235A (en) * | 1997-06-26 | 1999-12-07 | Lockheed Martin Corporation | Method of fabrication for mercury-based quaternary alloys of infrared sensitive materials |
US11158749B2 (en) | 2017-02-24 | 2021-10-26 | First Solar, Inc. | Doped photovoltaic semiconductor layers and methods of making |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4116733A (en) * | 1977-10-06 | 1978-09-26 | Rca Corporation | Vapor phase growth technique of III-V compounds utilizing a preheating step |
US4468283A (en) * | 1982-12-17 | 1984-08-28 | Irfan Ahmed | Method for etching and controlled chemical vapor deposition |
US4566918A (en) * | 1983-09-13 | 1986-01-28 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Utilizing interdiffusion of sequentially deposited links of HgTe and CdTe |
-
1986
- 1986-07-28 US US06/851,255 patent/US4719124A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4116733A (en) * | 1977-10-06 | 1978-09-26 | Rca Corporation | Vapor phase growth technique of III-V compounds utilizing a preheating step |
US4468283A (en) * | 1982-12-17 | 1984-08-28 | Irfan Ahmed | Method for etching and controlled chemical vapor deposition |
US4566918A (en) * | 1983-09-13 | 1986-01-28 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Utilizing interdiffusion of sequentially deposited links of HgTe and CdTe |
Non-Patent Citations (2)
Title |
---|
"The Growth of Cdx Hg1-x Te Using Organometallics", by J. B. Mullin and S. J. C. Irvine, Journal of Vacuum Science and Technology, vol. 21, No. 1, (May/Jun. 1982) pp. 178-181. |
The Growth of Cd x Hg 1 x Te Using Organometallics , by J. B. Mullin and S. J. C. Irvine, Journal of Vacuum Science and Technology, vol. 21, No. 1, (May/Jun. 1982) pp. 178 181. * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4904337A (en) * | 1988-06-06 | 1990-02-27 | Raytheon Company | Photo-enhanced pyrolytic MOCVD growth of group II-VI materials |
US5685905A (en) * | 1995-03-10 | 1997-11-11 | Shin-Etsu Handotai, Co., Ltd. | Method of manufacturing a single crystal thin film |
US5998235A (en) * | 1997-06-26 | 1999-12-07 | Lockheed Martin Corporation | Method of fabrication for mercury-based quaternary alloys of infrared sensitive materials |
US6208005B1 (en) | 1997-06-26 | 2001-03-27 | Lockheed Martin Corporation | Mercury-based quaternary alloys of infrared sensitive materials |
US11158749B2 (en) | 2017-02-24 | 2021-10-26 | First Solar, Inc. | Doped photovoltaic semiconductor layers and methods of making |
US11791427B2 (en) | 2017-02-24 | 2023-10-17 | First Solar, Inc. | Doped photovoltaic semiconductor layers and methods of making |
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